Polymers of acrylates and methacrylates of bicyclic phosphites and bicyclic phosphates



United States Patent PQLYMERS 0i ACRi LATEE? AND METHAQRY- LATES GiBECYCHC PHQSPEETE AND BE- CYCLIC THQSPHATES William D. Einmons,Huntingdon Valiey, and William S. Wadsworth, in, Willow Grove, Pat,assignors to Rollin & Haas Company, Philadelphia, Pa, a corporation ofDelaware No Drawhig. (higinal application Jan. 19, 196i, den No. 83,613.Divided and this appiicatio-n Mar. 14, 1962., Ser. No. 179,8il1

7 Claims. (Cl. 26tl--80.5)

This application is a division of Serial No. 83,613, filed January 19,1961.

This invention relates to compounds of Formula I:

0 H2 0 wherein R is a methyl group or a hydrogen atom, and n is aninteger from 0 to 1.

Typical of the valuable compounds of the invention are the following:

Methacryloxymethyl bicyclic phosphite Acryloxymethyl bicyclic phosphiteMethacryloxymethyl bicyclic phosphate Acryloxymethyl bicyclic phosphateThe bicyclic phosphates and phosphites of this invention are valuablemonomers which are polymerizable to form useful polymers. The bicyclicphosphites and phosphates are also pesticides. The polymers are usefulas coatings, as additives to lubricating oils and in various otherapplications.

The bicyclic phosphites of the invention can be prepared by a number ofconvenient methods. A preferred method of preparation comprises reactingthe bicyclic phosphites of Formula II:

01120 OHCHgCCHgO-P with a compound of Formula III:

31 CHg=( J-O 0X wherein R is defined above, and X is a halogen atom,such as bromine and preferably chlorine.

The reaction between the compound of Formula H and Formula III isspontaneous and exothermic. The reaction is preferably performed in thepresence of an inert organic solvent. Examples of useful solventsinclude benzene, toluene, xylene, acetone, methylethyl ketone, diethylketone, ethyl acetate, and mixtures of such solvents.

The temperature may vary from 0 C. to 50 C. or over, but it is muchpreferred, especially when high yields are desired, to maintain thetemperature in the range from 20 C. to 10 C.

During the reaction between Compounds II and III, it is preferable touse a base acceptor to take up the hydrogen halide liberated. Useful forsuch purposes are organic bases, such as an amine like pyridine,triethylamine, or an inorganic base like sodium hydroxide, sodiumcarbonate, sodium bicarbonate, or lime; or basic reacting salts likesodium acetate. In the reaction between Compounds II and III, it isquite satisfactory to employ stoichiometric amounts or" the twocompounds,

3,155,639 Patented Nov. 3, 1964 although greater or smaller amounts maybe employed if desired.

For best results, it is also desirable to employ a polymerizationinhibitor, such as hydroquinone and other equivalent acrylate andmethacrylate inhibitors. The use of an inhibitor is especiallyrecommended when temperatures over 25 C. are employed. After thereaction is completed, the reaction medium is filtered and the prodnotis obtained by removal of solvent, preferably under reduced pressure.

The bicyclic phosphates of the invention can readily be prepared fromthe bicyclic phosphite by oxidation thereof. The method of preparationof the phosphates comprises oxidizing the phosphites, preferably insolution, with an oxidizing agent, preferably in stoichiometric amount.As oxidizing agents, there may be used any of the typical organicperoxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide,t-butyl hydroperoxide, methyl ethyl ketone peroxide, and the like;oxidizing peracids such as peracetic acid, perbenzoic acid, performicacid and equivalent oxidizing agents.

Since the oxidation of the bicyclic phosphite is an exothermic reaction,it is advisable to keep the temperature preferably below C., such as inthe range of 10 to 50 C. The reaction is terminated when the exothermsubsides.

Suitable solvents in which the bicyclic phosphites may be dissolvedduring the oxidation reaction include a wide variety of organicsolvents, such as lower hydrocarbon solvents of aliphatic, naphthenic oraromatic type, such as benzene, toluene, xylene, mineral spirits,ethers, ketones, such as acetone, methyl ethyl ketone, dioxane andtetrahydrofuran; esters such as ethyl, butyl and amyl acetates, andethoxyethyl acetate; chlorinated hydrocarbons, such as carbontetrachloride, chloroform and ethylene dichloride, and the like.

The compounds of the invention are useful in numerous applications. Theyare valuable pesticides; they are effective bactericides, fungicides andinsecticides. The compounds are monomers which are polymerizable bythemselves to form homopolymers or, even more advantageously, with otherethylenically unsaturated compounds, such as polymerizable vinylidenecompounds to form valuable linear copolymers.

Typical of the polymerizable vinylidene or monoethylenically unsaturatedcompounds that may be employed to produce copolymers include: vinylothers, such as vinyl methyl ether, vinyl butyl ether, vinyl octylether, vinyl dodecyl ether, or vinyl stearyl ether; allyl others, suchas allyl butyl ether, allyl vinyl ether, allyl octyl ether, or allyldecyl ether; aciylates, such as methyl acrylate, ethyl acrylate, butylacrylate, octyl acrylate, or stearyl acrylate; methacrylates, such asmethyl methacrylate, ethyl methacrylate, butyl methacrylate, or octylmethacrylate; acrylamides or methacrylarnides, such as methylacrylarnide, methyl methacrylamide, butyl acrylamide, or butylmethacrylamide; vinyl esters such as vinyl acetate, vinyl butyrate, orvinyl stearate; allyl esters, such as allyl butyrate, allyl palmitate,or allyl stearate; maleates such as butyl maleate, octyl maleate, ordodecyl maleate; itaconates, such as octyl itaconate, dodecyl itaconate,or octadecyl itaconate; styrenes, such as styrene or vinyl toluene, ormaleic anhydride, acrylonitrile, or the like.

The amount of compounds of Formula I in the copolymers of this inventionmay be widely varied, amounts in the range of 5 to yielding highlysatisfactory results. The remainder may comprise one or more of othercopolymerizable vinylidene or rnonoethylenically unsaturated compoundspreviously mentioned. Preferred copolymers are those comprising from 5to 20 mole percent of at least one monomer of Formula A preferred groupof comonomers comprise the alkyl esters of acrylic and methacrylic acidhaving from 1 to 18 carbon atoms in the alkyl group. Increasing theproportion of methacrylic and/or acrylic acids in the polymers promotesthe solubility of the monomers of the invention. Apparently by virtue ofthe presence of the phosphate or phosphite groups in the monomer, thepolymers exhibit a combination of unusual and beneficial properties.

The homopolymerization or the copolymerization of the compounds ofFormula I may be conducted as a bulk, solution or dispersion process, asdesired. It is preferable that the polymerization be conducted in therange of to 125 C. or higher. Preferably, a polymerization initiator isused, such as one or more of the peroxidic or the azo initiators, whichact as free radical catalysts. Typical organic peroxides include benzoylperoxide, acetyl peroxide, p-menthane hydroperoxide, and the like;typical azo catalysts include azodiisobutyronitrile,dimethyldiazoisohutyronitrile and azodiisobutyramide. In aqueoussystems, ammonium, sodium or potassium persulfates are also convenientalone or in combination with an organic peroxide.

The polymer or copolymer is a viscous or solid product that can beapplied from a solution in a thin film to a flat metal, glass or Woodensurface.

The following examples are given for purposes of illustration and arenot intended as a limitation to the invention. All parts given are byweight.

Example 1 Hydroxymethyl bicyclic phosphite, 262.4 parts (1.5 moles), ischarged to a two-liter, three-necked, roundbottom flask fitted with astirrer, thermometer, condenser and dropping funnel. One thousand partsof methylene chloride are added and the mixture stirred until solutionis complete. The solution is chilled and 155 parts (1.5 moles) ofmethacryl chloride is added. To the rapidly stirred solution there arethen added 152 parts (1.5 moles) of triethylamine at 20 C. When additionis complete, the mixture is allowed to come to room temperature slowlywith rapid stirring. The mixture is suctionfiltered and stripped atreduced pressure.

The residue remaining from the stripping is recrystallized fromisooctane yielding over an 80% yield of White crystallinemethacryloxymethyl bicyclic phosphite of a melting point of 108 C.

Example 2 Hydroxymethyl bicyclic phosphite, 262.4 parts (1.5 moles) ischarged to a reaction flask with 152 parts of triethylamine and onethousand parts methylene chloride. The temperature is maintained at C.and 135.8 parts of acryl chloride is added with rapid stirring. When theaddition is complete, the mixture is allowed to come to room temperatureslowly. The mixture is suction filtered and the product is collected bystripping the filtrate at mm. of pressure. A crystalline product isobtained which is acryloxymethyl bicyclic phosphite.

Example 3 There are dissolved 24.8 parts of methacryloxymethyl bicyclicphosphite in 75 parts of alcohol; the alcoholic solution is treated with3.4 parts of a H 0 solution while the reaction flask is cooled in an icebath. Methacryloxymethyl bicyclic phosphate comes out as a precipitate;it is removed by such filtration and recrystallized from ethanol.

Example 4 Likewise, from the oxidation of acryloxymethyl bicyclicphosphite with H 0 there is obtained acryloxymethyl bicyclic phosphate.

Example 5 A miXtlll'e Containing 60 pa ts methyl methacrylate,

A 30 parts methacryloxymethyl bicyclic phosphite and 10 partsmethacrylic acid was polymerized at C. using a 0.01%azodiisobutyronitrile as a catalyst. There is obtained a clear, hardpolymer which exhibits strong adhesion to glass surfaces.

A sample of this polymer was placed in a flame; the polymer charred butdid not burn.

(b) Another copolymer is obtained by substituting for the methacrylicacid in part (a) an equivalent amount of acrylic acid.

(0) Another copolymer is obtained by substituting ethyl methacrylate formethyl methacrylate in part ([1).

(cl) Another copolymer is obtained from the polymerization of parts ofmethyl methacrylate, 10 parts of methacrylic acid and 20 parts ofmethacryloxymethyl bicyclic phosphate.

(e) Another copolymer results from substituting 30 parts acryloxymethylbicyclic phosphate for the methacryloxymethyl bicyclic phosphate in part(a).

(f) Another copolymer results from the polymerization of 40 parts ofacryloxymethyl bicyclic phosphite and methacrylic acid.

(g) A homopolymer is obtained by the procedure of part (a) by omittingthe methyl methacrylate and the methacrylic acid.

Example 6 (a) A charge comprising 485.1 parts of methyl methacrylate,202.9 parts of ethyl acrylate, 17.85 parts of methacryloxymethylbicyclic phosphite, 1.78 parts of benzoyl peroxide, and 53.6 parts ofmethyl cellosolve is added with stirring in the course of two hours to aglass reaction vessel containing 810.6 parts of toluene. The toluene ismaintained at reflux during the addition. The reaction is carried outunder an atmos here of nitrogen.

Two, four, and six hours after the polymerization has started, thereaction is recatalyzed with 0.7 gram of additional benzoyl peroxidewhile maintaining the temperature at reflux. The heating is continuedfor a total of eight hours after which time the solution is diluted toapproximately 39% resin solids by the addition of toluene. The finalresin is a clear viscous solution.

The resin when applied to cold rolled steel gives a film havingexcellent hardness, adhesion, gloss and flexibility.

(b) In a similar manner, there is substituted in part (a)methacryloxybicyclic phosphite by an equivalent portion ofacryloxymethyl bicyclic phosphite. The clear viscous resinous solutionWhich is obtained is applied onto a steel panel to provide an effectivecoating.

(0) In part (a) methacryloxymethyl bicyclic phosphite is substituted byan equivalent proportion of the corresponding phosphate.

(d) Likewise, in part (a) methaeryloxymethyl bicyclic phosphite issubstituted by acryloxymethyl bicyclic phosphate.

The polymers and copolymers of the invention are useful as lubricatingoil additives, especially for improving the lubricity and the anti-wearproperties of the lubricating oils. In such lubricating oils, thepolymers of the invention may be incorporated in amounts from about 0.01to about 10% by Weight, preferably 0.1 to 0.25% by weight.

We claim:

1. A copolymer of a compound of the Formula I:

wherein R is selected from the group consisting of a methyl group and ahydrogen atom, and

n is an integer from O to 1,

with at least one other copolymerizable monoethylenically unsaturatedcompound said compound of Formula I being 5 to of the weight of thecopolymer, and said copolymer ranging from a viscous liquid to a solid.

5 6 2. The polymer of claim 1 in which the monomer is one othercopolymerizable vinylidene unsaturated commethacryloxymethyl bicyclicphosphite. pound selected from the group consisting of acrylic acid,

3. The polymer of claim 1 in which the monomer is methacrylic acid, andalkyl esters of these acids. acryloxymethyl bicyclic phosphite. 7. Apolymer of a compound of claim 1 with methyl 4. The polymer of claim 1in which the monomer is 5 methacrylate and methacrylic acid.methacryloxymethyl bicyclic phosphate. 1

5. The polymer of claim 1 in which the monomer is Referemes Cried m thefile of tms patent acryloxymethyl bicyclic phosphate. ITED STATESPATENTS 6. A polymer of a compound of claim 1 with at least 2,643,261 Mk et 1 June 23 1 53

1. A COPOLYMER OF A COMPOUND OF THE FORMULA I:
 7. A POLYMER OF ACOMPOUND OF CLAIM 1 WITH METHYL METHACRYLATE AND METHACRYLIC ACID.